Functionalization of Enzymatically Synthesized Rigid Poly(itaconate)s via Post-Polymerization Aza-Michael Addition of Primary Amines

Alice Guarneri, Viola Cutifani, Marco Cespugli, Alessandro Pellis, Roberta Vassallo, Fioretta Asaro, Cynthia Ebert, Lucia Gardossi*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

2 Citations (Scopus)

Abstract

The bulky 1,4-cyclohexanedimethanol was used as co-monomer for introducing rigidity in lipase synthetized poly(itaconate)s. Poly(1,4-cyclohexanedimethanol itaconate) was synthetized on a 14 g scale at 50 °C, under solvent-free conditions and 70 mbar using only 135 Units of lipase B from Candida antarctica per gram of monomer. The mild conditions preserved the labile vinyl group of itaconic acid and avoided the decomposition of 1,4-cyclohexanedimethanol, both observed in chemical polycondensations. Experimental and computational data show that the enzymatic polycondensation proceeds despite the low reactivity of C 1 of itaconic acid. The rigid poly(1,4-cyclohexanedimethanol itaconate) was investigated in the context of aza-Michael addition of hexamethylenediamine and 2-phenylethylamine to the vinyl moiety. The enzymatically synthesized linear poly(1,4-butylene itaconate) was studied as a comparison. The two oligoesters (Molecular Weights ranging from 720 to 2859 g mol −1 ) reacted on a gram scale, at 40–50 °C, at atmospheric pressure and in solvent-free conditions. The addition of primary amines led to amine-functionalized oligoesters but also to chain degradation, and the reactivity of the poly(itaconate)s was influenced by the rigidity of the polymer chain. Upon the formation of the secondary amine adduct, the linear poly(1,4-butylene itaconate) undergoes fast intramolecular cyclization and subsequent degradation via pyrrolidone formation, especially in the presence of hexamethylenediamine. On the contrary, the bulky 1,4-cyclohexanedimethanol confers rigidity to poly(1,4-cyclohexanedimethanol itaconate), which hampers the intramolecular cyclization. Also, the bulkiness of the amine and the use of solvent emerged as factors that affect the reactivity of poly(itaconate)s. Therefore, the possibility to insert discrete units of itaconic acid in oligoesters using biocatalysts under solvent-free mild conditions opens new routes for the generation of bio-based functional polymers or amine-triggered degradable materials, as a function of the rigidity of the polyester chain. (Figure presented.).

Original languageEnglish
JournalAdvanced Synthesis and Catalysis
DOIs
Publication statusE-pub ahead of print - 27 Mar 2019

Fingerprint

Amines
Rigidity
Polymerization
Cyclization
1,6-diaminohexane
Lipases
Polycondensation
Acids
Monomers
Degradation
Functional polymers
Biocatalysts
Candida
Atmospheric pressure
Polyesters
Molecular weight
itaconic acid
Decomposition
Pyrrolidinones
Polymers

Keywords

  • 1,4-cyclohexanedimethanol
  • aza-Michael addition
  • bio-based polyesters
  • enzymatic polycondensation
  • itaconic acid
  • primary amines

Cite this

Guarneri, Alice ; Cutifani, Viola ; Cespugli, Marco ; Pellis, Alessandro ; Vassallo, Roberta ; Asaro, Fioretta ; Ebert, Cynthia ; Gardossi, Lucia. / Functionalization of Enzymatically Synthesized Rigid Poly(itaconate)s via Post-Polymerization Aza-Michael Addition of Primary Amines. In: Advanced Synthesis and Catalysis. 2019.
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title = "Functionalization of Enzymatically Synthesized Rigid Poly(itaconate)s via Post-Polymerization Aza-Michael Addition of Primary Amines",
abstract = "The bulky 1,4-cyclohexanedimethanol was used as co-monomer for introducing rigidity in lipase synthetized poly(itaconate)s. Poly(1,4-cyclohexanedimethanol itaconate) was synthetized on a 14 g scale at 50 °C, under solvent-free conditions and 70 mbar using only 135 Units of lipase B from Candida antarctica per gram of monomer. The mild conditions preserved the labile vinyl group of itaconic acid and avoided the decomposition of 1,4-cyclohexanedimethanol, both observed in chemical polycondensations. Experimental and computational data show that the enzymatic polycondensation proceeds despite the low reactivity of C 1 of itaconic acid. The rigid poly(1,4-cyclohexanedimethanol itaconate) was investigated in the context of aza-Michael addition of hexamethylenediamine and 2-phenylethylamine to the vinyl moiety. The enzymatically synthesized linear poly(1,4-butylene itaconate) was studied as a comparison. The two oligoesters (Molecular Weights ranging from 720 to 2859 g mol −1 ) reacted on a gram scale, at 40–50 °C, at atmospheric pressure and in solvent-free conditions. The addition of primary amines led to amine-functionalized oligoesters but also to chain degradation, and the reactivity of the poly(itaconate)s was influenced by the rigidity of the polymer chain. Upon the formation of the secondary amine adduct, the linear poly(1,4-butylene itaconate) undergoes fast intramolecular cyclization and subsequent degradation via pyrrolidone formation, especially in the presence of hexamethylenediamine. On the contrary, the bulky 1,4-cyclohexanedimethanol confers rigidity to poly(1,4-cyclohexanedimethanol itaconate), which hampers the intramolecular cyclization. Also, the bulkiness of the amine and the use of solvent emerged as factors that affect the reactivity of poly(itaconate)s. Therefore, the possibility to insert discrete units of itaconic acid in oligoesters using biocatalysts under solvent-free mild conditions opens new routes for the generation of bio-based functional polymers or amine-triggered degradable materials, as a function of the rigidity of the polyester chain. (Figure presented.).",
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author = "Alice Guarneri and Viola Cutifani and Marco Cespugli and Alessandro Pellis and Roberta Vassallo and Fioretta Asaro and Cynthia Ebert and Lucia Gardossi",
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Functionalization of Enzymatically Synthesized Rigid Poly(itaconate)s via Post-Polymerization Aza-Michael Addition of Primary Amines. / Guarneri, Alice; Cutifani, Viola; Cespugli, Marco; Pellis, Alessandro; Vassallo, Roberta; Asaro, Fioretta; Ebert, Cynthia; Gardossi, Lucia.

In: Advanced Synthesis and Catalysis, 27.03.2019.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Functionalization of Enzymatically Synthesized Rigid Poly(itaconate)s via Post-Polymerization Aza-Michael Addition of Primary Amines

AU - Guarneri, Alice

AU - Cutifani, Viola

AU - Cespugli, Marco

AU - Pellis, Alessandro

AU - Vassallo, Roberta

AU - Asaro, Fioretta

AU - Ebert, Cynthia

AU - Gardossi, Lucia

PY - 2019/3/27

Y1 - 2019/3/27

N2 - The bulky 1,4-cyclohexanedimethanol was used as co-monomer for introducing rigidity in lipase synthetized poly(itaconate)s. Poly(1,4-cyclohexanedimethanol itaconate) was synthetized on a 14 g scale at 50 °C, under solvent-free conditions and 70 mbar using only 135 Units of lipase B from Candida antarctica per gram of monomer. The mild conditions preserved the labile vinyl group of itaconic acid and avoided the decomposition of 1,4-cyclohexanedimethanol, both observed in chemical polycondensations. Experimental and computational data show that the enzymatic polycondensation proceeds despite the low reactivity of C 1 of itaconic acid. The rigid poly(1,4-cyclohexanedimethanol itaconate) was investigated in the context of aza-Michael addition of hexamethylenediamine and 2-phenylethylamine to the vinyl moiety. The enzymatically synthesized linear poly(1,4-butylene itaconate) was studied as a comparison. The two oligoesters (Molecular Weights ranging from 720 to 2859 g mol −1 ) reacted on a gram scale, at 40–50 °C, at atmospheric pressure and in solvent-free conditions. The addition of primary amines led to amine-functionalized oligoesters but also to chain degradation, and the reactivity of the poly(itaconate)s was influenced by the rigidity of the polymer chain. Upon the formation of the secondary amine adduct, the linear poly(1,4-butylene itaconate) undergoes fast intramolecular cyclization and subsequent degradation via pyrrolidone formation, especially in the presence of hexamethylenediamine. On the contrary, the bulky 1,4-cyclohexanedimethanol confers rigidity to poly(1,4-cyclohexanedimethanol itaconate), which hampers the intramolecular cyclization. Also, the bulkiness of the amine and the use of solvent emerged as factors that affect the reactivity of poly(itaconate)s. Therefore, the possibility to insert discrete units of itaconic acid in oligoesters using biocatalysts under solvent-free mild conditions opens new routes for the generation of bio-based functional polymers or amine-triggered degradable materials, as a function of the rigidity of the polyester chain. (Figure presented.).

AB - The bulky 1,4-cyclohexanedimethanol was used as co-monomer for introducing rigidity in lipase synthetized poly(itaconate)s. Poly(1,4-cyclohexanedimethanol itaconate) was synthetized on a 14 g scale at 50 °C, under solvent-free conditions and 70 mbar using only 135 Units of lipase B from Candida antarctica per gram of monomer. The mild conditions preserved the labile vinyl group of itaconic acid and avoided the decomposition of 1,4-cyclohexanedimethanol, both observed in chemical polycondensations. Experimental and computational data show that the enzymatic polycondensation proceeds despite the low reactivity of C 1 of itaconic acid. The rigid poly(1,4-cyclohexanedimethanol itaconate) was investigated in the context of aza-Michael addition of hexamethylenediamine and 2-phenylethylamine to the vinyl moiety. The enzymatically synthesized linear poly(1,4-butylene itaconate) was studied as a comparison. The two oligoesters (Molecular Weights ranging from 720 to 2859 g mol −1 ) reacted on a gram scale, at 40–50 °C, at atmospheric pressure and in solvent-free conditions. The addition of primary amines led to amine-functionalized oligoesters but also to chain degradation, and the reactivity of the poly(itaconate)s was influenced by the rigidity of the polymer chain. Upon the formation of the secondary amine adduct, the linear poly(1,4-butylene itaconate) undergoes fast intramolecular cyclization and subsequent degradation via pyrrolidone formation, especially in the presence of hexamethylenediamine. On the contrary, the bulky 1,4-cyclohexanedimethanol confers rigidity to poly(1,4-cyclohexanedimethanol itaconate), which hampers the intramolecular cyclization. Also, the bulkiness of the amine and the use of solvent emerged as factors that affect the reactivity of poly(itaconate)s. Therefore, the possibility to insert discrete units of itaconic acid in oligoesters using biocatalysts under solvent-free mild conditions opens new routes for the generation of bio-based functional polymers or amine-triggered degradable materials, as a function of the rigidity of the polyester chain. (Figure presented.).

KW - 1,4-cyclohexanedimethanol

KW - aza-Michael addition

KW - bio-based polyesters

KW - enzymatic polycondensation

KW - itaconic acid

KW - primary amines

U2 - 10.1002/adsc.201900055

DO - 10.1002/adsc.201900055

M3 - Article

JO - Advanced Synthesis and Catalysis

JF - Advanced Synthesis and Catalysis

SN - 1615-4150

ER -